Dis- and polyazo dyestuffs



nrs- AND POLYAZO DYESTUFFS Philippe Grandjean, Basel, and Walter Wehrli,

Switzerland, assignors to Sandoz A. G., land, a Swiss firm No Drawing. Application March 27, 1953, Serial No. 345,249

Claims priority, application Switzerland April 4, 1952 6 Claims. (Cl. 260-166) Riehen, Basel, Switzerwherein each of x and y is one of the numerals and 1, and wherein each of R1, R2, R3 and R4 stands for a radical of the benzene or naphthalene series which may be substituted for example by halogen atoms, lower alkyl groups, lower alkoxy groups, acylamino groups and/or nitro groups, said aminoazo compound containing at least two solubilizing groups such as SO3H and/or COOH, with one mol of a dicarboxylic acid halide corresponding to the formula ZOC--CH=OCOZ it (II) wherein each Z stands for C1 or Br, and Y stands for hydrogen or CH3.

According to the present invention, dyestutfs with superior properties are obtained by condensing two mols of a mixture of two difierent non-metallizable aminoazo compounds corresponding to Formula I supra, with one mol of a dicarboxylic acid halide which corresponds to the formula ZOCCH=CCOZ ii III) wherein Z has the precedingly-indicated significance, and A signifies H, Cl, Br or CH3, the reactants being so selected that the product possesses the number of solubilizing groups necessary to impart water-solubility thereto.

Suitable unsaturated dicarboxylic acid halides which, according to the present invention, serve for the joining together of the two aminoazo compounds of formula (I), comprise the dichlorides and dibromides of fumaric acid, maleic acid, methyl-fumaric acid, methyl-maleic acid, chloro-fumaric acid and bromo-fumaric acid, etc. In order to compensate for possible losses due to hydrolysis, it is advantageous to employ the dicarboxylic acid halides in slight excess.

In carrying out the process of the invention, the two aminoazo compounds (I) are dissolved in water, and then the dicarboxylic acid halide (III) is added, preferably at low temperature (from about 0 C. to about 30 C.). The condensation mixture is thoroughly stirred, care being taken by the addition of acid-binding agents-such for example as sodium bicarbonate, sodium carbonate, sodium hydroxide, the corresponding lithium or potassium compounds, alkaline earth metal oxides or carbonates, or appropriate tertiary organic amines such as nited States Patent r 2,746,954 Patented May 22, 1956 N,N-dimethylaminobenzeneto constantly neutralize liberated hydrogen halide. The dicarboxylic acid halide may be diluted by an indifferent solvent, such for example as benzene, methylbenzene, chlorobenzene, carbon tetrachloride or chloroform. The condensation is completed when free amino can no longer be detected. The resultant reaction product is in part already precipitated, and the remainder is isolated from the reaction solution by salting-out or, in some cases, by acidification, the precipitate being then filtered, washed it necessary, and

dried. It contains as integrating constituent a component of the formula RQT wherein R is the radical of the one aminoazo compound (I) acylated in the amino group, T is the radical of the other aminoazo compound (I) acylated in the amino group, and Q is the radical of the dicarboxylic acid corresponding to the dicarboxylic acid halide (III). The two symmetrical products of the formulae R-Q-R and TQT are also present.

The two dilferent aminoazo compounds (I) may be joined together in the 1:1 proportion by the dicarboxylic acid halide (III). However, valuable dyestutfs are also obtained with other mixture proportions, as for example when the condensation products are prepared from one mol of dicarboxylic acid halide (III) and two parts of two difierent aminoazo compounds (I) which are present in the 4:1, 3:1, 2:1, 1:2,1:3 or 1:4 proportion.

The new water-soluble, non-metallizable dyestuffs of the present invention may be defined as corresponding to the formula wherein x, y, R1, R2, R3, R4 and A have the hereinbeforerecited significances, and at least one of R1, R2, R3 and R4 carries at least one solubilizing group, and wherein the moieties R and R" are not identical although they correspond'to the same type formula. The present invention comprises products which are superior to the symmetrical dyestuifs of the aforementioned copending application, as regards afiinity to vegetable fibers and as regards the fastness of their dyeings to wet treatments. The dyeings obtainable according to the present invention comprise dyeings with shades which as regards color tone, depth of color and vividness, can not be obtained'with the symmetrical dyestufis of the said copending application.

The following examples set forth representative exemplary embodiments of the invention, and are intended to be illustrative only and not at all limitative. In these examples, the parts and percentages are by weight, and the temperatures are in degrees centigrade.

Example 1 348 parts (0.75 mol) of the aminomonoazo compound prepared by coupling diazotized Z-aminonaphthalene-4,8-disulfonic acid with l-amino-B-acetylaminobenzene, and 69.3 parts (0.25 mol) of 4'-amino-1,l-azobenzene-4-sulfonic acid are together dissolved at room temperature (about 20-30) in water with the addition of aqueous sodium hydroxide solution. Into the resultant solution there are then simultaneously added, dropwise and with good stirring, a mixture of 76.5 parts (0.5 mol) of fumaric acid dichloride and parts of benzene, and such quantity of aqueous sodium carbonate solution as is necessary to keep the reaction weakly alkaline throughout. After all the fumaric acid dichloride has been added, stirring of the reaction solution is continued until no more free amino can be detected. The formed dystutf mixture is then separated from the warm solution with the aid of sodium chloride, filtered off and dried. It is a yellow powder which dyes cotton and fibers of regenerated cellulose in greenish yellow shades which are very fast to light. The asymmetrical component of the mixture corresponds to the formula SOaH N'H-CO-CH:

The identical dyestutf is obtained if, in the foregoing, the fumaric acid dichloride is replaced by 0.5 mol of fumaric acid dibromide.

By replacing the 0.75 mol of the aminomonoazo compound by 0.9 mol thereof and correspondingly replacing the 0.25 mol of 4'-amino-l,l'-azobenzene-4-sulfonic acid by 0.1 mol thereof, and otherwise proceeding according to the first paragraph of this example, a valuable dyestud of high substantivity is obtained.

Dyestuffs with similar properties are also obtained when, while following the procedure outlined in this example,

on the one hand the 2-aminonaphthalene-4,S-disulfonic acidused in preparing the first initial aminomonoazo compoundis replaced by an other aminonaphthalene disulfonic acid, such for examule as 2-aminonaphthalene- 6,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, Z-aminonaphthalene-l,S-disulfonic acid, or l-aminonaphthalene-3,6-disulfonic acid and/or the 1-amino-3- acetylaminobenzene by another amine of the benzene series, such for example as aminobenzene, 1-amino 2- methylbenzene, 1-amino-3-methylbenzene, 1-arnino-3-ethylbenzene, l amino 2,5 dimethylbenzene, 1 amino- Z-methoxybenzene, l-amino-2-rnethoxy-5-methylbenzene, 1 amino 2 methoxy 5 acetylaminobenzene, l-amino- 2,5-dimethoxybenzene, 1-amino-2,S-diethoxybenzene, lamino-3-f0rmylaminobenzene, l-amino-3-propionylaminobenzene, l-amino-3-benzoylaminobenzene, and/or on the other hand the second component of the starting mixture--the 4-amino-1,l'-azobenzene-4-sulfonic acidis replaced by the equivalent quantity of an aminoazo compound obtained by coupling a diazotized aminobenzene-rnonosulfonic acid, such for example as 1-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid, 1-amino-4-methylbenzene-3-sulfonic acid, l-amino2,4-dichlorobenzene-6-sulfonic acid, l-amino-4-bromobenzene- 2-sulfonic acid, l-amino-4-nitrobenzene-Z-sulfonic acid, 1-amino-2-carboxybenzene-4-sulfonic acid, 1-amino-2-carboxybenzene-S-sulfonic acid, or a diazotized aminonaphthalene-monosulfonic acid such for example as l-aminonaphthalene-4-sulfonic acid, l-andnonaphthalene-S-sulnaphthalene-7-sulfonic acid or Z-aminonaphthalene-S-sulfonic acid, with one of the precedingly-mentioned amines of the benzene series.

Example 2 pound, prepared by coupling diazotized 2-aminonaphthalene-6,8-disulfonic acid with l-amino-Z-methoxy-S- methylbenzene are together dissolved neutral in water with the addition of aqueous sodium hydroxide solution, after which condensation with 76.5 parts (0.5 mol) of fumaric acid dichloride is carried out after the manner described in Example 1. The isolated resultant dyestufi mixture is a yellow powder and dyes cotton and fibers of regenerated cellulose in pure yellow shades which are very fast to light. The asymmetrical component of the mixture corresponds to the formula Dystuffs with similar properties are obtained when, in the preparation of either or both of the aforesaid aminomonoazo compounds, the 2-aminonaphthalene-6,8- disulfonic acid is replaced'by one of the aminonaphthalene-disulfonic acids mentioned in Example 1 and/or the 1-amino-3-acetylaminobenzene or the l-amino-2-methoxy-- S-methylbenzene, respectively, is replaced by one of the amines of the benzene series mentioned in Example 1,

be different from each other.

Example 3 270 parts (0.5 mol) of the aminomonoazo compound, prepared by coupling diazotized Z-aminonaphthalene- 4,8-disulfonic acid with l-amino-3-methylbenzene, condensing the thus-obtained-intermediate with 4-nitro-benzene-l-carboxylic acid chloride and then reducing the nitro group to the amino group, and 225.5 parts (0.5 mol) 55 of the aminomonoazo compound, prepared by coupling diazotized 2-aminonaphthalene-6,S-disulfonic acid with l-amino-Z-methoxy-S-methylbenzene are together dis-. solved neutral in water with the addition of aqueous, so-. dium hydroxide solution, and thencondensation carried out according to the data of Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride. The thus-produced dyestufi mixture is, after isolation, a yellow powder and dyes cotton and fibers of regenerated cellulose in yellow. shades which are very fast to light. The asymmetrical 65 component of the mixture corresponds to the formula OCH:

Dystuflis with similar properties are obtained when, in

with the proviso that the two starting compounds must;

the preceding paragraph, the Z-aminobenzene-l-carboxylic acid radical in the first of the recited aminomonoazo compounds is replaced by the 3-aminobenzene-1-carboxylic acid group (i. e. when, in lieu of the 4-nitrobenzene-1- carboxylic acid chloride, use is made of 3-nitrobenzene- 5 l-carboxylic acid chloride).

Example 4 222.3 parts (0.45 mol) of the aminomonoazo compound,

803E: CH;

prepared by coupling 2-aminonaphthalene-6,8-disulfonic acid with 1amino2methoxy5-acetylaminobenzene, and

261.3 parts (0.55 mol) of the aminodisazo compound, prepared by coupling diazotized 4-amino-l,1-azobenzene- 4,3'-disulfonic acid with l-amino-B-methylbenzene, are together dissolved neutral in water with the addition of aqueous sodium hydroxide solution, after which condensation is carried out with 76.5 parts (0.5 mol) of fumaric acid dichloride in accordance with the data of Example 1. The resultant dyestutl mixture is a brown powder and dyes cotton and fibers of regenerated cellulose in orange shades which are of excellent dischargeability and fastness to light. The asymmetrical component of the mixture corresponds to the formula SO H OCH;

H038 SOaH HWS WGW ylbenzene used in preparing the aminodisazo compound is replaced by one of the amines of the benzene series mentioned in Example 1.

Example 5 158 parts (0.33 mol) of the aminodisazo compound, prepared by coupling diazotized 4'-amino-l,1'-azobenzene- 4,3-disulfonic acid with l-amino-3-methylbenzene, and

1-amino-3-methylbenzene, are together dissolved in water with the addition of aqueous sodium hydroxide solution, and then condensation carried out according to the data of Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride. The resultant dyestuif mixture is a darkbrown powder which dyes cotton and fibers of regenerated cellulose in yellowish brown shades of good dischargeability and fastness to light. The asymmetrical component of the mixture corresponds to the formula I Dyestufis with similar properties are obtained when, in preparing the aminodisazo compound in the preceding paragraph, the l-amino-B-methylbenzene is replaced by one or more times by one of the amines of the benzene series mentioned in Example 1.

Example 242.8 parts (0.4 mol) of the aminodisazo compound, prepared by the alkaline coupling of disazotized 4-aminol,l'-az0benzene-4,3'-disulfonic acid with 2-amino-5-hydroxynaphthalene-7sulfonic acid, and 285 parts (0.6 mol) of the amino-diazo compound, prepared by coupling diazotized 4-amino-l,1'-azobenzene-4,3-disulfonic acid with 1amino-3-rnethyl-benzene, are together dissolved in water CH! SOQH with the addition of aqueous sodium hydroxide solution, after which condensation is carried out according to Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride. The thus-prepared dyestuff mixture is, after isolation, a dark-brown powder and dyes cotton and fibers of regenerated cellulose in light-fast scarlet-red shades. The asymmetrical component of the mixture corresponds to the formula CH; SOaH Dyestuffs with similar properties are obtained when, in the preparation of the first of the aminodisazo compounds, according to the preceding paragraph, the 4-amino-1,1'- azobenzene-4,3'-disulfonic acid is replaced by 4'-amino- 1,l'-azobenzene-4-sulfonic acid or by 4'-N-( -aminobenzoyl)-amino-l,1'-azobenzene-4,3-disulfonic acid and/ or on the other hand the 1-amino-3-methylbenzene, used in preparing the second aminodisazo compound, is replaced by one of the amines of the benzene series mentioned in Example 1.

Thev following examples, set up in tabular form, further illustrate the invention. The procedure is in each case analogous to that of Example 1. The resultant dyeings are characterized by good dischargeability and fastness to light.

TABLE Condensation with Fumaric Acid Dichloride or Dibromida Example Shade of Dyeing N o. p on Cotton First Component Second Component (3) 7 4-amino-1,l-azobenzene-4,3'-disulionic acid 1- 2-aminonaphthalene-4;8-disulfonic acid 1- orange.

amino-2-mcthoxy-5-methylbenzenc. gmino-li-methylbenzene l-amino-3-methylcnzcne. 8 2-aminonaphthalene-4,8-disulfonic acid 1- aminobenzcnc 1-aminonaphthalene-6-sulionic greenish olive. amino'3-acetylaminobenzene. acid 1 aminonaphthalene 6 sulfonic acid T 2 amino 8 hydroxynaphthalene 6 snlfonic aci 9 .do l-aminohenzene-(i-sulfonic acid -v l-aminonaph Do.

izhalene-6-sulf0nic acid l-aminonaphthalene T 2 amino hydroxynaphthalene 7 sulfonic aci 10 baminobenzene-Mulfonicacid l-ami1io2-meth- 2-aminonaphthalene-6,8-disulfonie acid 1- yellowish orange.

oxy-fi-methylbenzene. amino-3-methylbenzene l-amino-Z-mcthoxyfi-methylbenzene. 11 Z-aminonaphthalene-6,8-disulfonic acid ldo orange.

amino-2-rnethoxy-fi-methylbenzene. 12 2 aminonaphthalene-4,8-disulfonic acid 1 2 aminonaphthalene-4,S-disulfonie acid 1 Do.

amino-2-ethoxy-5-benzoylaminobenzene. amino 3 acetylaminobenzene 1- amino 3 methylbenzene. 13 Z-aminonaphthalene-6,8-disulfonic acid 1- 2-aminonaphthalene-6,8-disulionic acid aml- Do.

amino-ii-methylbcnzene ll-amino-Z-methoxynobenzene 1-an1ino-3-methylbenzeno. frmcthylbenzene. 14 2-aminonaphthalene-6,8-disulfonic acid 1- 4-amino-l,l'-azobcnzene-4,3'-disulionic acid 1- yellowish orange.

gmino-2-methylbenzene 1-amino-3methylamin0-3-met-hylbenzene.

enzene. 15 2amin0naphthalene-4,8'-disulfonic acid 1- 4-amino-l,l-azobenzene-4,3'-disulfonic acid 1- orange.

amino-B-methylbenzene l-amino-Z-mcthoxyamino-2,5-dimethylbcnzene. 5-methylbenzcne. 16 do 4-amino-1,l-azobenzene-*i,3'-disnlfonic acid 1- D0.

amino-2-methoxy-E-methylbenzene. 17 2 aminonaphthalene 6,8 disullonic acid 1 2 aminonaphthalene 6,8 disulionic acid 1 reddish brown.

amino-3-methylhenzene l-amino-S-methylamino-3-acetylaminobenzene L-amino-B- benzene l-amino-2-methoxy-5-methylbenmethylbenzene. zene. i8 4-amino-1,1-azobenzene-4,3-disulionic acid 1- 4-amino-1,l'-azobcuzene-4,3-disu1fonic acid 1- yellowish brown.

amino-3-methylbenzene l-amino-S-methylamino-S-methylbenzene 1-amino-2-methoxybenzene. fi-methylbenzene. 19 l-aminobenzeneA-sulionic acid l-aminonaph- 4-amino 1,1-azobenzene-4,3-disulionic acid 1- Do.

thalenc-G-sulfonic acid l-amino-3-methylbenamino-3-methylbenzene. zone. 20 4'-amino-1,1'-azobenzene-4,3-disulfonic acid 1- do yellow.

amino-B-methylbenzene, condensed'with 4-nitrobenzene-l-carboxylic acid chloride and reduced to the amino compound. 21 Z-aminonaphthalene-6,8-disu1fonic acid 1- do Do.

amino2-methoxy-5-butyrylaminohenzene. 22 2-armnonaphthalene-4,8-disulf0nic acid ll-arninobcnzene-i-sulionlc acid l-aminonaphgreenish olive.

amin0-3-(4'-mei;hyl)-benzoylaminobenzene.

thalene 1-aminonaphthalene-6-su1ionie acid T 2 amino 8 hydroxynaphthalene 6 sulfonic aoi fastness to light.

In Examples 7 to 22, the ratio of the first mixture com- S0 11 OCH;

products obtained in selected illustrative ceding tabular examples follows:

OCH: CHI

Example 11 501E OCH:

Example 13 ponent to the secondcomponent may be 1:1. However, other ratios, such as 4:1, 3:1, 2:1, 1:2, 1:3 and 1:4 may be employed, with the proviso that in every case two mols of the mixture of first and second components are condensed with one mol of dicarboxylic acid halide.

The formulae of the asymmetrical component of the ones of the pre- SOa Example 14 S0311 CH: OCH:

(1)011: IOaH I SO H Example 16 In all the examples, the binding of the liberated hydrogen halide may, with equal success, be effected with sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, lithium carbonate, calcium hydroxide, calcium carbonate, magnesium oxide, or N,N-dimethylaminobenzene, instead of with sodium carbonate.

Example 23 100 parts of cotton are introduced at 80 into a dyebath containing a solution of 1 part of anhydrous sodium E018 NH-C O-CH;

carbonate and 0.5 part of dyestuff obtainable according to Example 2 (first paragraph) in 2000 parts of water.

S0311 OCH:

The dyebath is slowly heated to boiling, 20 parts of anhydrous sodium sulfate are added and the bath then 80311 OCH:

allowed to cool slowly to The dyed material is withdrawn, rinsed with cold water and dried. There is thus SOsH CH: CH;

SOsH

OCHs $03K 3. The trisazo dyestutf which corresponds to the formula 0 CH: CIHz $0311 4. The tetrakisazo dyestuli which corresponds to the formula 5. The tetrakisazo dyestutf which corresponds to the formula SOzH SOaH

obtained a yellow dyeing of excellent fastness to light and dischargeability.

SOgH OCH:

The dyestufis of the other examples may be used for dyeing in essentially analogous manner.

Having thus disclosed the invention what is claimed is:

l. A water-soluble, non-metallizable azo dyestutf which 65 corresponds to the formula l(R1N=N-) r z-N=N]=R:N=NR4NH- i 0 wherein each x and each y is one of the numerals 0 and 1, each R1, R2, R3 and R4 stands for a radical selected 6. The tetrakisazo dyestutf which corresponds to the formula OCH; SOaH References Cited in the file of this patent UNITED STATES PATENTS 2,104,595 Schirm Jan. 4, 1938 2,646,338 Kappeler July 21, 1953 2,673,198 Grandjean et al. Mar. 23, 1954 FOREIGN PATENTS 418,455 Great Britain Oct. 25, 1934 504,489 Belgium July 31, 1951 

1. A WATER-SOLUBLE, NON-METALLIZABLE AZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 